JPH0324658B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for developing a silver halide photographic light-sensitive material, and more particularly to a method for developing a photographic light-sensitive material that can be handled in an environment that can be essentially called a bright room. In the printing plate-making process, in response to the desire to perform the contact exposure process (so-called return process) using a relatively low-sensitivity photosensitive material in a bright room, in recent years, silver halide has been used as a photosensitive element and Photographic materials that can be handled in what can be called a "room environment" have been developed. This is achieved by exposing a photosensitive material whose sensitivity to visible light has been extremely reduced (approximately 1/10 ⁴ of conventional light) to a light source containing a large amount of Shiba rays under safe light that contains virtually no ultraviolet rays. be done. On the other hand, the so-called return process involves not only simple one-sheet contact return (using a single developed film as an original, contact exposure and development of the return photosensitive material to convert a negative image to a positive image); Advanced image conversion work called characters is performed. These cut-out characters are the parts of printed matter where ink is covered in a halftone pattern (halftone dots) and the parts where ink is spread all over the paper (solid parts).・It refers to parts such as symbols.More specifically, to describe how to make cut-out characters in the photolithography process, as shown in Figure 1, a transparent or translucent pasting base 3 (usually a number
10 μm thick polyethylene terephthalate (polyethylene terephthalate is used) is pasted with a developed film (halftone dot original) 4 on which halftone dots are formed, and similarly a so-called line image positive image such as letters and symbols is formed on the pasting base 1. Developed film (line drawing original) 2
The pasted version and the superimposed version are the manuscript.
The emulsion surface of the photosensitive material 5 for return is brought into close contact with the halftone dot image area, and exposed and developed to form blank portions of line drawings in the halftone dot image. An important point in this process is that the halftone dot image and the line drawing must undergo negative/positive image conversion according to their halftone dot area and line width, respectively. For example 50%
A halftone image with a black area of 50% white area,
A line drawing with a black line width of 50 μm must be accurately converted to a white line width of 50 μm. However, as is clear from FIG. 1, the halftone image is exposed by directly contacting the emulsion surface of the return photosensitive material, whereas the line image is exposed using the halftone dot original 4 (usually having a thickness of about 110 μm). )
and pasting base 3 for the halftone original (several 100 μm
The photosensitive material for return is exposed to light through the intermediate layer (thickness). In other words, the line image becomes blurred exposure via a transparent or semi-transparent spacer of several 100 μm and is applied to the photosensitive material for return. For this reason, if a normal exposure amount (an exposure amount that faithfully converts the halftone dot area from negative to positive) is applied, the white line width of the line image will become narrower due to the effect of blurring exposure. On the other hand, if the exposure amount is reduced in order to reduce the influence of blurred exposure and to faithfully convert the line width of a line image from negative to positive, the halftone dot area becomes thin due to insufficient exposure. Not only the photosensitive material but also the exposure light source greatly contributes to this phenomenon. That is, if the exposure light source is small enough to be called a point light source, the degree of blurred exposure will be reduced. However, in the photosensitive material for bright room use as in the present invention, an exposure device with a large amount of light must be used.
The light source is larger than that of conventional darkroom type exposure equipment, which causes deterioration in the quality of printed characters. Until now, there have been almost no reports on means to eliminate such deterioration in the quality of cut-out characters, and there have been few reports on methods to eliminate such deterioration in the quality of cut-out characters. ), the purpose of which was completely different from that of the previous one, so there was no knowledge of what measures should be taken. Regarding silver halide photosensitive materials that can be handled in a bright room, see, for example, JP-A-56-125734 and JP-A-56-125734.
Examples of emulsions in which grains are formed by adding a large amount of rhodium salt are described in No. 149030 and No. 56-149031, but these known examples do not describe any technique for improving the quality of cut-out characters. In addition, these known examples disclose that polyalkylene oxides are added to the developer, but as is clear from the results of the comparative sample included in Example 1, which will be described later, it is not possible to add polyalkylene oxides to the developer alone. Even if polyalkylene oxides are added, improvement in cutout character quality cannot be achieved. On the other hand, in recent years, many attempts have been made to obtain image quality comparable to that of lithography through rapid and stable processing, but there is a growing demand for the same rapid and stable processing to be performed in the character extraction process, which is an advanced image conversion process. It's getting stronger. Until now, the specific technology to meet this request was not well known. An object of the present invention is to provide a method for quickly obtaining a good cutout character image using a stable processing liquid. The above objects of the present invention are such that at least 80 mol% of the total silver halide consists of silver chloride and the average grain size is
0.4 μm or less, and contains a water-soluble rhodium salt of 1 x 10 ^-6 mol or more per mol of silver at any time before the completion of the first ripening of emulsion production, and the emulsion Silver halide photosensitive material, characterized in that the layer or at least one hydrophilic colloid layer contains a polyalkylene oxide or a derivative thereof having a molecular weight of at least 600 in an amount of 1×10 ^-5 to 1×10 ^-2 mol per mol of silver. The material is dihydroxybenzene-based developing agent from 0.05 to
0.5 mol/contains, the auxiliary developing agent is 0.05 g/or less, and the free sulfite ion concentration is 0.25 mol/
Contains more than 20 5 or 6 nitroindazoles
This was achieved by treatment with a developer containing a sufficient amount of alkali to raise the pH of the developer to 10.5 or higher. The silver halide in the silver halide photosensitive material used in the present invention is composed of silver chloride, silver chlorobromide, silver iodochloride, and silver iodobromochloride, and preferably at least 80 mol% is composed of silver chloride. It is preferable that 90 mol% or more consists of silver chloride, especially
Preferably, 95 mol% or more consists of silver chloride. The average grain size of silver halide is preferably 0.4 μm or less, particularly preferably 0.3 μm or less.
Average grain size is a term commonly used and easily understood by those skilled in the field of silver halide photographic science. Particle size means the particle diameter in the case of particles that are spherical or can be approximated to a sphere. When the particle is cubic, the particle size is defined as the edge length x √4/π. Determined by algebraic mean or geometric mean based on the average particle projected area. For more information on how to determine average particle size, see CEMees and TH James: The theory of the photographic process,
3rd ed.p.36-p.43, (1966, published by McMillan)
Please refer to . The water-soluble rhodium salt used in the present invention is typically rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc., but complex salts can also be used. The time for adding the rhodium salt in the present invention is limited to before the end of the first ripening during emulsion production, and it is particularly desirable to add it during grain formation, and the amount added is 1 x 10 ^-6 mol or more per mol of silver. Desirably, more preferably 1×10 ^-5 or more, 5×10 ^-5 to 1×
A range of 10 ⁻³ is particularly preferred. In the present invention, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, the so-called controlled double-jet method. A silver halide emulsion with nearly uniform grain size can be obtained. Preferably, particle formation is carried out under acidic conditions.
Our experiments have shown that the effectiveness of the present invention decreases under neutral and alkaline conditions. The preferred pH range is 6 or less, more preferably 5 or less. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., single or copolymers thereof. Can be done. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.
As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples are U.S. Patent No. 2614928, U.S. Patent No. 3132945,
3186846, 3312553, British Patent No. 861414,
It is described in No. 1033189, No. 1005784, and Japanese Patent Publication No. 42-26845. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. In particular, polymers with some degree of compatibility with gelatin, such as acrylic acid,
Graft polymers with polymers such as methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate are preferred. Examples of these are U.S. Pat.
It is described in issues such as No. 2956884. Typical synthetic hydrophilic polymer substances include West German patent applications (OLS)
No. 2312708, U.S. Patent No. 3620751, U.S. Patent No. 3879205,
This is described in Japanese Patent Publication No. 7561/1973. The silver halide emulsion used in the method of the present invention may or may not be chemically sensitized. From the viewpoint of improving handling properties in a bright room, it is rather preferable that the film is not chemically sensitized. In the case of chemical sensitization, any one of ordinary sulfur sensitization, reduction sensitization, and gold sensitization or a combination thereof is used. The polyalkylene oxide compound used in the present invention is an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2
- oxide, such as butylene-1,2-oxide, preferably ethylene oxide.
Polyalkylene oxide consisting of units, water,
aliphatic alcohols, aromatic alcohols, fatty acids,
It includes condensates with compounds having at least one active hydrogen atom, such as organic amines and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides. That is, as polyalkylene oxide compounds, specifically, polyalkylene glycols polyalkylene glycol alkyl ethers polyalkylene glycol aryl ethers polyalkylene glycol (alkylaryl) ethers polyalkylene glycol esters polyalkylene glycol fatty acid amides polyalkylene Glycolamines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, etc. can be used. The molecular weight needs to be 600 or more. The number of polyalkylene oxide chains is not limited to one in the molecule, and two or more may be included. In that case, the individual polyalkylene oxide chains may consist of fewer than 10 alkylene oxide units, but
The total number of alkylene oxide units in the molecule must be at least 10. If there is more than one polyalkylene oxide chain in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention is preferably 14 or more.
Contains up to 100 alkylene oxide units. Specific examples of the polyalkylene oxide compounds used in the present invention are as follows. Polyalkylene oxide compound example-1 HO (CH ₂ CH ₂ O) ₉₀ H −2 C ₄ H ₉ O (CH ₂ CH ₂ O) ₁₅ H −3 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₅ H − 4 C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₅ H −5 C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₄₀ H −6 C ₈ H ₁₇ CH=CHC ₈ H ₁₆ O (CH ₂ CH ₂ O ) _15H Polyalkylene oxide compounds described in JP-A-50-156423, JP-A-52-108130, and JP-A-53-3217 can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more. When these polyalkylene oxide compounds are added to a silver halide emulsion, they are added as an aqueous solution of an appropriate concentration or dissolved in a low boiling point organic solvent that is miscible with water, and added at an appropriate time before coating, preferably. It can be added to the emulsion after chemical ripening. It may be added to non-photosensitive hydrophilic colloid layers, such as intermediate layers, protective layers, filter layers, etc., instead of being added to the emulsion. The amount of the polyalkylene oxide compound used in the present invention is preferably in the range of 1×10 ⁻⁵ mol to 1×10 ⁻² mol per mol of silver halide. Furthermore, in the present invention, it has been discovered that the quality of printed characters can be further improved when a bentriazole compound and/or a mercapto compound, which are commonly used as antifoggants, are used in combination. These compounds were effective only when included in photosensitive materials. This effect was not simply an effect of preventing fog, nor was it an effect of making the characteristic curve sharper, but rather improving the quality of drawn characters. One of the preferred compounds includes one or more substituents selected from alkyl groups (methyl, ethyl, heptyl, etc.), alkoxy groups, halogen atoms, acyl groups, acylamino groups, carbamoyl groups, sulfamoyl groups, aryl groups, etc. Of the benzotriazole compounds which may be substituted with , alkyl-substituted benzotriazoles having 1 to 3 carbon atoms were particularly effective. And its effective addition amount range is 1×10 ^-4 per mole of silver.
to 1×10 ^-2 mol, particularly preferably 5
The amount was from ×10 ⁻⁴ to 5×10 ⁻³ mol. Another preferred compound was represented by the following general formula. In the formula, M represents a hydrogen atom, _-NH4 group, or an alkali metal atom; , represents an optionally substituted aralkyl group, and Z forms a 5-membered heterocycle (e.g., tetrazole, triazole, imidazole, thiadiazole) or a 5-membered heterocycle fused with a benzene ring (e.g., benzimidazole, benzthiazole, benzoxazole) These heterocycles represent alkyl groups,
Alkoxy group, carboxy group, sulfo group, hydroxyl group, amino group, nitro group, halogen atom,
It may be substituted with a carbamoyl group, an alkylthio group, a mercapto group, etc. Preferred among these are compounds in which Z is represented by tetrazole, triazole, thiadiazole, benzimidazole, or benzthiazole, and most preferred are tetrazole compounds. Specific examples of preferred compounds are shown below.

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The effective addition amount range of the compound was from 5 x 10 ^-5 to 5 x 10 ^-3 moles per mole of silver. In the photographic emulsion of the present invention, as a filter dye,
Alternatively, a water-soluble dye may be contained for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes,
Included are styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent No. 584609, British Patent No. 1177429, Japanese Patent Application Laid-open No. 1985-85130,
No. 49-99620, No. 49-114420, U.S. Patent
No. 2274782, No. 2533472, No. 2956879, No.
No. 3148187, No. 3177078, No. 3247127, No. 3148187, No. 3177078, No. 3247127, No.
No. 3540887, No. 3575704, No. 3653905, No.
It is described in No. 3718472. The photographic emulsion of the present invention may contain an inorganic or organic hardening agent. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether,
N,N'-methylenebis-[β-(vinylsulfonyl)propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-
triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6
-Hydroxytriazinylated gelatin and the like can be used alone or in combination. Specific examples include U.S. Patent No. 1870354, U.S. Patent No. 2080019, U.S. Patent No.
No. 2726162, No. 2870013, No. 2983611, No. 2983611, No.
No. 2992109, No. 3047394, No. 3057723, No.
No. 3103437, No. 3321313, No. 3325287, No. 3321313, No. 3325287, No.
No. 3362827, No. 3539644, No. 3543292, British Patent No. 676628, No. 825544, No. 1270578, German Patent No. 872153, No. 1090427, Japanese Patent Publication No. 34-7133,
It is described in No. 46-1872, etc. The photographic emulsion of the present invention may contain various known surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties. For example, saponins (steroids), polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, sugars. alkyl esters, nonionic surfactants such as urethanes or ethers; triterpenoid saponins, alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates Carboxy groups such as esters, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. , sulfo group,
Anionic surfactants containing acidic groups such as phospho groups, sulfate ester groups, phosphate ester groups; amino acids,
Aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines,
Amphoteric surfactants such as amine imides and amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium,
Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Specific examples of these surfactants are listed in the U.S. patent.
No. 2240472, No. 2831766, No. 3158484, No.
No. 3210191, No. 3294540, No. 3507660, British Patent No. 1012495, No. 1022878, No. 1179290, British Patent No.
No. 1198450, Japanese Unexamined Patent Publication No. 117414, US patent
No. 2739891, No. 2823123, No. 3068101, No.
No. 3415649, No. 3666478, No. 3756828, British Patent No. 1397218, US Patent No. 3133816, No. 3441413,
Same No. 3475174, No. 3545974, No. 3726683, Same No.
No. 3843368, Belgian Patent No. 731126, British Patent
No. 1138514, No. 1159825, No. 1374780, Tokko Akira
No. 40-378, No. 40-379, No. 43-13822, U.S. Patent No. 2288226, No. 2944900, No. 3253919,
No. 3671247, No. 3772021, No. 3589906, No.
No. 3666478, No. 3754924, West German patent application
This is described in OLS1961638, Japanese Patent Application Laid-open No. 50-59025, etc. The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for purposes such as improving dimensional stability. For example alkyl (meta)
Acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate,
(meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin,
Styrene etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used.
For example, US Patent No. 2376005, US Patent No. 2739137,
No. 2853457, No. 3062674, No. 3411911, No.
No. 3488708, No. 3525620, No. 3607290, No.
No. 3635715, No. 3645740, British Patent No. 1186699,
The one described in No. 1307373 can be used. The developing agents used in the developer of the present invention include dihydroxybenzene-based developing agents, 1-phenyl-3-pyrazolidone-based developing agents, p-aminophenol-based developing agents, etc. Phenyl-3-pyrazolidones and dihydroxybenzenes or p-aminophenols and dihydroxybenzenes) can be used. The light-sensitive material of the present invention may also be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone. In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone,
Examples of 1-phenyl-3-pyrazolidone-based developing agents include methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, and 1-phenyl-3-pyrazolidone.
4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-
Examples include phenyl-3-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, etc., and p-aminophenol, N-methyl-p-aminophenol, etc. are used as p-aminophenol developing agents. . A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of a contagious developer, sodium formaldehyde bisulfite may be used, which provides almost no free sulfite ions in the developer. As the alkaline agent for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, diethanolamine, triethanolamine, etc. are used. The pH of the developer is usually set to 9 or higher, preferably 9.7 or higher. The developer solution may also contain organic compounds known as antifoggants or development inhibitors. Examples include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione; azaindenes, e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) Tetrazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide,
Examples include sodium 2-mercaptobenzimidazole-5-sulfonate. The developer for processing the photosensitive material of the present invention does not contain any auxiliary developing agent (for example, 1-phenyl-3-pyrazolidones or p-aminophenols) or contains only 0.05 g or less, and dihydroxybenzene is used as the main developing agent. A developer containing 0.05 to 0.5 mol/(especially 0.1 to 0.4 mol/) of
The induced sulfite ion concentration is 0.25 mol/or more, and 5- or 6-nitroindazole is 20 mg/
or more, and has a pH of 10.5 or more (especially 11.5 or more)
This is a developer containing a sufficient amount of alkali to Among these, it is preferable to use dihydroxybenzenes (especially hydroquinone) alone without containing an auxiliary developing agent. This developer can quickly form a return image with excellent cutout quality when cutting out characters using the photosensitive material of the present invention, and is extremely stable as it can contain a large amount of sulfite ions. It is. It is preferable that the developer that can be used in the present invention contains the same type of polyalkylene oxide as described above as a development inhibitor. For example, molecular weight 1000~
10000 polyethylene oxide etc. 0.1~10
It can be contained within a range of g/g/. It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetate acid, triethylenetetraamine hexaacetate acid, diethylenetetraamine pentaacetate acid, etc. as a water softener to the developer that can be used in the present invention. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. The fixer can also contain a complex of ethylenediaminetetraacetic acid and trivalent iron ions as a sulfurizing agent. Processing temperature and processing time are set appropriately, but usually18
Processing temperatures of .degree. C. to 50.degree. C. are suitable, while rapid processing of 15 to 120 seconds using so-called automatic processors is preferred. The light-sensitive material of the present invention has a halogen composition, an average particle size, and an amount of rhodium salt added, each of which has a predetermined value, so that it has good handleability in a bright room, which is required as a return light-sensitive material, and high sensitivity when printed with a light source rich in ultraviolet rays. It can give a high-contrast image, and since it contains a polyalkylene oxide compound or its derivative, the line width of the line image can also be faithfully converted from negative to positive at the exposure dose that faithfully converts the halftone dot area to negative/positive in character cutting work. It has the unpredictable effect of being able to perform positive conversion. Further, the developing method of the present invention, in which the photosensitive material of the present invention is processed with a developer having the above-described specific composition, makes it possible to quickly form cut-out character images of excellent image quality, and furthermore, the developer is stable. Therefore, it has the excellent advantage of being able to be used for a long period of time. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Liquid: 600 ml of water, 18 g of gelatin, PH3.0 Liquid: 200 g of AgNO ₃ , 800 ml of water Using the above liquids and solutions, seven types of emulsions A to G were prepared by the following method. 1 Emulsion A (Br5 mol%, grain size 0.25μ, Rh1
×10 ^-4 mol/mol silver) Solution _A : 7 g of KBr, 69 g of NaCl, 40 mg of NH ₄ RhCl ₆ ,
The two liquids were added simultaneously at a constant rate over 30 minutes to 800 ml of water kept at 42°C. After removing soluble salts from this emulsion using a conventional method well known in the art, gelatin was added as a stabilizer without chemical ripening.
-Methyl-4-hydroxy-1,3,3a,7
- Tetraazaindene was added. The average grain size of this emulsion was 0.25 μm, the yield of the emulsion was 1 kg, and the amount of gelatin contained was 60 g. 2 Emulsion B (Br15 mol%, grain size 0.25μ, Rh1
×10 ^-4 mol/mol silver) _B solution: KBr21g, NaCl62g, NH ₄ RhCl ₆ 40
mg, water 800ml Emulsion 3 was prepared in the same manner as Emulsion _A , using Solution _B instead of Solution A. 3 Emulsion C (Br30 mol%, grain size 0.25μ, Rh1
×10 ^-4 mol/mol silver) _C solution: KBr42g, NaCl52g, NH ₄ RhCl ₆ 40
mg, water 800ml Emulsion C was prepared in the same manner as Emulsion _A , using Solution _C instead of Solution A. 4 Emulsion D (Br15 mol%, grain size 0.45μ, Rh1
×10 ^-4 mol/mol silver) Emulsion D was prepared in the same manner as Emulsion B except that the temperature of the liquid was changed to 65°C. Emulsion D has the same composition as Emulsion B except that the grain size is 0.45 μm. 5 Emulsion E (Br5 mol%, grain size 0.25μ, Rh1
×10 ^-4 mol/mole silver, added after washing with water) Solution _E : 7 g of KBr, 69 g of NaCl, 800 ml of water After removing grain formation and soluble salts using Solution _E in the same manner as Emulsion A, add gelatin and add 1% more After adding 4 c.c. (equivalent to 40 mg) of NH ₄ RhCl ₆ aqueous solution, 2-methyl-4-hydroxy-1,3,3a was added as a stabilizer without chemical ripening.
7-tetraazaindene was added. 6 Emulsion F (Br5 mol%, grain size 0.25μ, Rh1
×10 ^-7 mol/mol silver) _F solution: KBr7g, NaCl69g, NH ₄ RhCl ₆ 0.04
mg, water 800ml Emulsion B was prepared in the same manner as Emulsion A, using _F in place of _A. 7 Emulsion G (Br5 mol%, grain size 0.25μ, Rh2
×10 ^-6 mol/mol silver) _G solution: KBr 7 g, NaCl 69 g, NH ₄ RhCl ₆ 0.8 mg,
800 ml of water Emulsion G was prepared in the same manner as Emulsion _A , using Solution _G instead of Solution A. A hardener 2-hydroxy-4,6 is added to these emulsions.
-Dichloro-1,3-5-triazine sodium salt and polyalkylene oxide compound-7
1×10 ^-4 mol/mol silver was added to the polyethylene terephthalate film to give an amount of 4.5 g of silver per 1 m ^{2 .}
It was applied so that The film samples prepared in this manner are referred to as Film A to Film G, respectively. Furthermore, a hardening agent and polyalkylene oxide compound-19 were added per 50g of emulsion to emulsion A.
A film sample coated in the same manner with the addition of 16 mg (1.0 x 10 ^-4 mol/mol silver) is referred to as Film H. Furthermore, a film sample was obtained by coating Emulsion A with a hardening agent but without adding a polyalkylene oxide compound. After exposure using a P-607 printer manufactured by Dainippon Screen Co., Ltd. using an original with the configuration shown in Figure 1, FG-1 was applied with Lith developer HS-1 manufactured by Fuji Photo Film Co., Ltd.
Put it in a 25L automatic processor and wait for the optimum development time (27℃, 1
minutes and 40 seconds). Further, the following developer was placed in an automatic processor FG-25RA manufactured by Fuji Photo Film Co., Ltd., and processed at the optimum developing time (38° C., 20 seconds). (Developer) Potassium bromide 2.0g Potassium hydroxide 20g Potassium carbonate 35g Potassium sulfite 80g Hydroquinone 20g Triethylene glycol 30g Polyethylene glycol (molecular weight 4000) 2.0g 5-nitroindazole 0.1g Add water 1 (PH11.7) Results are shown in Table 1.

[Table] The cutout image quality 5 in Table 1 is when an original as shown in Figure 1 is used and properly exposed so that 50% of the halftone dot area becomes 50% of the halftone dot area on the photosensitive material for return.
This refers to the image quality in which characters with a width of 30 μm are reproduced, and the image quality is very good. On the other hand, cut-out character image quality 1 refers to an image quality that can only reproduce characters with a width of 150 μm or more when given the same appropriate exposure, and is poor cut-out character quality, with a sensory evaluation of 4 to 2 between 5 and 1. A rank was established. A value of 2 or higher is a practical level. As is clear from Table 1, AgCl80% or more,
It can be seen that good drawing quality is exhibited only when the rhodium salt is 10 ^-6 mol/mol silver or more, added before the end of the first ripening, and in the presence of the polyalkylene oxide compound. Example 2 Liquid: 1000 ml of water, 20 g of gelatin, PH=4.0. Liquid: 200g of AgNO ₃ , 600ml of water. Liquid: KBr4.2g, NaCl75g, _RhCl3 20mg, water 600ml. The two liquids were added simultaneously at a constant rate over a period of 30 minutes into an aqueous gelatin solution kept at 45°C. After removing the soluble salts from this emulsion by a conventional method well known in the art, gelatin was added to the emulsion and 2-methyl-4-hydroxy-1, 2-methyl-4-hydroxy-1,
3,3a,7-tetraazaindene was added.
The average grain size of this emulsion was 0.28 μm, the yield of the emulsion was 1 kg, and the amount of gelatin contained was 70 g. This emulsion was added with a hardening agent, 2-hydroxy-4,6-
After adding dichloro-1,3,5-triazine sodium salt, it was coated on a polyethylene terephthalate film at a silver content of 4.5 g per m ² . The film sample prepared in this way is referred to as film J. Preparation of film K: When preparing a sample using the same method as J, polyalkylene oxide compound-17
A film sample of the present invention containing 2×10 ^-4 mol/mol Ag was prepared and designated as film K. Preparation of film L: When preparing a sample using the same method as J, polyalkylene oxide compound-17
A film sample of the present invention containing 2 x 10 ^-4 mol/mol Ag and 3 x 10 ^-3 mol/mol Ag of 5-methylbenzotriazole was prepared and designated as film L. Preparation of film M: Example of polyalkylene oxide compound when preparing a sample using the same method as J.
17 to 2×10 ^-4 mol/mol Ag and 1-phenyl-5-mercaptotetrazole to 4×10 ^-4 mol/mol
A film sample of the present invention containing molar Ag was prepared and designated as film M. Preparation of film N: Example of polyalkylene oxide compound when preparing a sample using the same method as J.
17 to 2 x 10 ^-4 mol/mol Ag and 5-methylbenzotriazole 3 x 10 ^-3 mol/mol Ag and 1-phenyl-5-mercaptotetrazole 4
A film sample of the present invention containing ×10 ⁻⁴ mol/mol Ag was prepared and designated as film N. After exposing with a P-607 printer made by Dainippon Screen using the original with the configuration shown in Figure 1, it was developed using an FG25RA automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) with the following seven types of developer composition. ,
Fixed, washed with water, and dried. Furthermore, in order to compare the stability of the developer, the developer was left in an automatic processor for 4 days and then developed in the same manner.

【table】

【table】

[Table] The term "appropriate development time" as used herein refers to the development time at which the development temperature is 32° C. and the development time is taken every 5 seconds to give the best cutout character image quality for the combination of the developer and the film. The cutout character image quality 5 here refers to when a document as shown in attached figure 1 is properly exposed so that 50% of the halftone dot area becomes 50% of the halftone dot area on the photosensitive material for return.
This refers to the image quality in which characters with a width of 30 μm are reproduced, and is a very good cutout character image quality. On the other hand, cutout character image quality 1 refers to an image quality that can only reproduce characters with a width of 150 μm or more when given the same appropriate exposure, and is a poor cutout character image quality. The sensitivity after 4 days is a comparison of the exposure time required to provide proper exposure with the exposure time required when using a new solution, as described above. As is clear from Table 2, with film No. 1 (comparative sample), good cutout character image quality could not be obtained with either developer. On the other hand, sample film No. 2 of the present invention,
For films No. 3, 4, and 5, the quality of the extracted characters was better than that for film No. 1 with all of the developers A, B, C, D, E, F, and G. It is clear that developer C, which has been cited as a particularly preferred developer, provides very good cutout character image quality. Developer solution D contains 1-phenyl-3-pyrazolidone as an auxiliary developing agent.
0.2g/contains, and it is clear that the quality of cut-out characters is inferior to that of developer C. Also, developer E
Since the sulfite ion concentration is low, the developer sensitivity decreases significantly after aging for 4 days, and a stable developer cannot be obtained. Developer F has a lower pH than Developer C,
The cutout character image quality is worse than development C, and the development time is longer. Furthermore, in developer G, 5-
This is the case when 5-methylbenzoliazole is used instead of nitroindazole, and the quality of cut-out characters is not as good as that of developer C. Therefore, developer C provides good cutout character image quality with a short development time and is a stable developer.
It is clear from Table 2 that particularly favorable results are obtained in the case of .

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between an original for which cut-out text is used and a photosensitive material for return. In the figure, 1 and 3 indicate a pasting base, 2 a film on which a line drawing positive image is formed (line drawing original), 4 a film on which a halftone dot image is formed (halftone dot original), and 5 a photosensitive material for return.

Claims (1)

[Claims] 1 At least 80 mol % of the total silver halide consists of silver chloride, the average grain size is not more than 0.4 μm, and at any time before the end of the first ripening of emulsion production, the concentration is less than 1 × 10 ^-6 per mole of silver. It has an emulsion layer containing a silver halide emulsion containing many water-soluble rhodium salts, and further contains a polyalkylene oxide or a derivative thereof having a molecular weight of at least 600 in the emulsion layer or other hydrophilic colloid layer. After exposing a silver halide photographic light-sensitive material containing 1 x 10 ^-5 to 1 x 10 ^-2 mol per mol, a dihydroxybenzene developing agent is contained in a range of 0.05 to 0.5 mol/mole, and an auxiliary developing agent is contained in an amount of 0 to 0.05 g/mole. and contains 0.25 mol/or more of free sulfite ions, 5- or 6-
- A developing method characterized by processing with a developer containing 20 mg/or more of nitroindazole and a sufficient amount of alkali to raise the pH to 10.5 or more.